Carbamate phosphates as compositions of matter and as insecticides and acaricides



United States Patent CARBAMATE PHOSPIIATES AS COMPOSITIONS OF MATTER ANDAS INSECTICIDES AND ACARICIDES Llewellyn W. Fancher and Donald G.Stolfey, Richmond, Richard C. Maxwell, Santa Clara, and Julius J. Menu,San Jose, Calif., assignors tp Staufier Chemical Company, a corporationof Delaware No Drawing. Filed July 24, 1959, Ser. No. 829,195

- 12 Claims. (Cl. 16722) In the above formula, Y and Y are sulfur oroxygen and at least one of Y and Y is sulfur, R is lower alkyl radical,R is the radical --CH CH and R and R are hydrogen, lower alkyl radicals,substituted or unsubstituted phenyl radicals or together form part of aheterocyclic ring. Those compounds are preferred wherein Y is sulfur. I

The compounds of the present invention can be made in accordance withthe following methods (code numbers have been assigned to each of thecompounds and are used in the balance of the specification):

Example 1.R2967. beta-(0,0-dimethyldithi0ph0sphoryl)-ethylcarbamate.-Into a 500 ml. round-bottomed flask equipped with astirrer, thermometer and condenser with a water trap were placed 12 g.of sodium-0,0-dimethyldithiophosphate and .150 ml. of toluene. The saltand toluene were dried by refluxing until no more water collected in thetrap. To the refluxing solvent, 6.2g. of

beta-chloroethylcarbamate was added, and refluxing was continued forfour hours. The reaction mixture was cooled, and the salts weredissolved in 50 ml. of water with stirring. The material was transferredto a separatory funnel, and the aqueous layer was removed and discarded.The toluene layer was washed with water twice more and then dried overmagnesium sulfate, filtered and the solvent was removed in a rotaryevaporator to give 8 g. (65% yield) of the light amber beta-(0,0-dimethyldithiophosphoryl)-ethylcarbamate, n 1.5033. Anal. forphosphorus: Calc., 12.63%. Found, 13.8%.

Example 2.R-3218. beta-(0,O-dimethyldithiophos- 'phoryl)-ethyl-N-butyl-N-methylcarbamate.ln essentialphosphate in 1500 ml. oftoluene to give 159.5 g. (97% yield) of nearly colorless liquid, 111.5158. Anal. for phosphorus: Calc., 11.33%. Found, 11.5%. Example4.-R3252 beta (0,0 diethyldithiophos- 2,998,347 Patented Aug 29, 1961phoryl) ethyl N pr0pylcarbamate.-In essentially the same manner asExample 1, beta-(0,0-diethyldithiophosicephoryl)-ethyl-N-propylcarbarnate was prepared from 16.6 g. ofbeta-chloroethyl-N-propylcarbamate and 25 g. ofsodium-0,0-diethyldithiophosphate in 150 ml. of toluene to give 24.5 g.(78% yield) of pale amber liquid, 12 1.4983. Anal. for phosphorus:Calc., 9.84%. Found, 9.37%.

Example 5.-R2972. beta (0,0 diethylthiolphosphoryl) -ethylcarbamate.lnessentially the same manner as Example 1,beta-(0,0-diethylthiolphosphoryl)-ethylcarbarnate was prepared from 6.2g. of beta-chloroethylcarbamate and 15 g. ofsodium-0,0-dimethylthiolphosphate in 150 ml. of toluene to give 5.5 g.(43% yield) of nearly colorless liquid, n 1.4668. Anal. for phosphorus:Calc., 12.04%. Found, 13.4%.

Example 6.R-3262. beta (0,0 diethyldithiophosphoryl)-ethyl-p-chlorocarbanilate.-Into a 500 ml. roundbottomed flask equippedwith a stirrer, thermometer and condenser were placed 11.7 g. ofbeta-chloroethyl-pchlorocarbanilate, 15 g. ofsodium-0,0-diethyldithiophosphate, 0.2 g. of potassium iodide and 150m1. of methylethylketone. The mixture was heated at reflux for sevenhours with stirring. The solvent was removed in a rotary evaporator, andml. each of water and ether were added with shaking. The aqueous layerwas discarded, and the ether layer was washed with water twice and thendried over magnesium sulfate, filtered, and the solvent was removed in arotary evaporator to give 12.0 g. (63% yield) of the brown liquid, 111.5504.

Example 7.R3292. beta (0,0 diethylthiolphosphoryl) -ethylcarbanilate.-Inessentially the same manner as in Example 6,beta-(0,0-diethylthiolphosphoryl)- ethylcarbanilate was prepared from19.9 g. of beta-chloroethylcarbanilate, 25 g. ofsodium-0,0-diethylthiolphosphate, 0.2 g. of potassium iodide and ml. ofmethylethylketone to give 18.6 g. (56% yield) of brown liquid whichpartially crystallized upon standing. Upon filtering, the brown filtratehad an index of refraction of n 1.5368.

In essentially the same manner as Example 1, the following carbamatephosphates were prepared:

Example Code No. Compound 8 R-3216 beta-(O, O-Dimethyldithiophosphoryl)-ethyl-N- propylcarbamate.

9 R-32l7 beta-(0, O-Dimethyldithiophosphoryl) ethyl-N- butylearbamate.

10 R-3260 beta (O, O Diethyldithiophosphoryl) ethyl N butylearbarnate.

11 R-3271 beta- (0, O Diethyldithiophosphoryl) -ethyl -Nbutyl-N-methylcarbamate.

12 R-3276 beta (0,0 Diethylthiolphosphoryl) -ethyl -N propylcarbamate.

13 R3278 beta (O, O Diethylthiolphosphoryl) ethyl N butylcarbamate.

l4 R-3279 beta- (0, O Diethylthiolphosphoryl) -ethyl-N,N

dimethylearbamate.

15 R-3280 beta (O, O Diethylthiolphosphoryl) ethyl Nbuty1-N-methy1earbamate.

16 R-3286 beta (0,0 Dirnethyldithiophosphoryl) ethylN,Ndi-i-propylearbarnate.

l7 R-3290 beta-(O, O-Diethyldithiophosphoryl)-ethyl-N,N-

di-i-propylcarbamate.

18 R-3293 beta: (0, O -Diethy1thiolphosphory1) -ethyl-N,N-

di-i-propylearbamate.

19 R-3294 beta-(O, O-Dimethy1dithiophospl1oryl)ethyl-N- pentylearbamate.

20 3-3299 beta (O, O Diethyldithiophosphoryl) -etl1yl N pentylcarbamate.

21 R-3300 beta (0,0 Diethylthiolphosphoryl) ethyl N pentylcarbamate.

no potassium iodide was used, the following carbamate phosphates wereprepared:

Example Code No. Compound 22 11-2964beta-(0,0-Dimethyldithiophosphoryl)-ethyl-N- methylcarbamate.

23 R-2960 beta-(0,0-Dlmethyldithlophosphoryl)-ethyl-N- ethylcarbamate.

24 R-2953 beta-(0,0-Dimethyldithiophosphoryl)-ethyl-N-i-propylcarbamate.

25 R-312l beta (0,0 Dimethyldithiophosphoryl) ethylN,N-dlmethylcarbamate.

26 R-3l32 beta (0,0 Dimethyldithiophosphoryl) ethyl N ,N-diethylcarbarnate.

27 R-31l4 beta (0,0 Dimethyldithiophosphoryl) ethyl carbanilate.

8 R-2965 beta (O, O Diethyldlthiophosphoryl) ethyl N methylcarbamate.

29 R-2961 beta (O, O Diethyldithiophosphoryl) ethyl N ethylcarbamate.

30 R-2954 beta-(0,0-Diethyldithiophosphoryl) -ethyl-N-ipropylcarbamate.

81 R-3l20 beta-(O, -Diethyldithiophosphoryl) -ethy1-N,N-dimethylcarbarnate.

32 R-3131 beta-(0, O-Diethyldithiophosphoryl)-ethyl, N, N-

diethylcarbamate.

33 R-3115 betta-(f-Diethyldithiophosphoryl) -etl1yl-caran a e.

34 12-2970 beta (O, O Diethylthiolphosphoryl) ethyl N methylcarbamate.

35 R-2966 beta (O, O Diethylthiolphosphoryl) ethyl N ethylcarbamate.

36 R-2957 beta- (0,0-Diethylthiolphosph0ryl) -ethy1-N-lpropylcarbamate.

37 R-3134 beta-(0,0-Diethylthiolphosphoryl) -ethy1-N,N-

diethylcarbamate.

In a similar manner, the following compounds were made:

The compounds have been tested as insecticides and as acaricidesaccording to the following methods:

Acaricidal Evaluation Test:' The two-spotted mite, Tetranychus telarius(Linm) is employed in tests for acaricides. Young Pinto bean plants areinfested with several hundred mites. Dispersions of test compounds areprepared by dissolving half a gram of the toxic material in tenmilliliters acetone. This solution is then diluted with water containing0.015% Vatsol (a sulfonate type wetting agent) and 0.005% Methocel(methyl cellulose) as emulsifiers, the amount of water being suflicientto give concentrations of active ingredient ranging from 0.25% to0.005%. The test suspensions are then sprayed on the infested Pinto beanplants. After seven and fourteen days, the plants are examined both forpostembryonic forms of the mite as well as eggs. The percentage of killis determined by comparison with control plants which have not beensprayed and the LD-SO value calculated using well-known procedures.LD-50 values are reported under the column 2 SM in Table l and PEindicates the post-embryonic forms.

Systemic Toxicity Evaluation Against Two-spotted Mites: Pinto beanplants in the primary leaf stage are placed in 250 ml. capacityErlenmeyer flasks, one plant per flask. A portion of the test compoundis dissolved in 10 ml. acetone. This solution is then diluted withdistilled water, the amount of water being sufficient to giveconcentrations of active ingredient ranging from one hundred parts permillion (ppm) to one part per million. The final volume of testdispersion per flask is 200 ml. The treated plants are infested withseveral hundred two-spotted mites, Tetranychus telarius (Linn.). Theresults are reported in the table under 2 SM Systemic.

After seven and fourteen days, the plants are examined both forpost-embryonic forms of the mite as well as eggs. The percentage of killis determined by comparison with control plants which have been placedin distilled water only. Again, the LD-SO value is calculated andreported under the column 2 SM Systemic" in Table 1.

Insecticidal Evaluation Tests: Five insect species are subjected toevaluation tests for insecticides:

(1) American cockroach (Roach)Periplanela americana (Linn) (2) Largemilkweed bug (:MWB)-0ncop'eltus fasciatus (Dallas) (3) Pea aphid(PiA)Macrosiphum pisi (Harris) (4) Confused flour beetle '(CFB)Triboliumconfusum (Duval) (5) House fly (HF)-Musca domeslica (Linn) The procedurefor insects 1, 2, 4 and 5 is similar to the miticidal testing procedure.Test insects are caged in cardboard mailing tubes 3%" in diameter and2%" tall. The cages are supplied with cellophane bottoms and screenedtops. Ten to twenty-five insects are used per cage. Food and water aresupplied in each cage. The confused flour beetles are confined in petridishes without food. The caged insects are sprayed with the activecompound at various concentrations. After twenty-four and seventy-twohours, counts are made to determine living and dead insects.

House fly evaluation tests differ in this respect: the toxicant isdissolved in a volatile solvent, preferably acetone, the active compoundis pipetted into a petri dish bottom, allowed to air dry and placed in acardboard mailing tube. Twenty-five female flies are caged in the tube.The flies are continuously exposed to the known residue of the activecompound in the cage. After twenty-four and seventy-two hours, countsare made to determine living and dead insects. The LD-50 values arecalculated using well known procedures.

The evaluation procedure on the pea aphid is as follows: Pinto beanplants are cut off above the root zone and the foliage is dipped in thedispersion of the active compound for fifteen seconds. The stems arethen inserted through a small slit in a plastic cover into a bottle ofwater. As soon as the foliage has dried, each plant is infested with tensecond or third instar aphids and caged on the plant. Mortalityobservations are made seventytwo hours later. Again, LD-50 values aredetermined p.p.m.

6. As a new compound: beta (0,0 diethylthiono pholinocarboxylate.

OFB,

percent percent Systemic,

55x555510 1x6x %5%x5xx5555555 x x55555 x5fixxx5xx5x 0 00 00 .0 0 0 00 00000 0 0 0 0 0 00 0 nu MWB, percent XX555 115 0II 55%5555555555 555555555555555555 0 0 0 .0 0 0 .0 0 0 0 .0 0 0 0 0 0w0 0w0 0 0 0 0 .0 0 0 0 00 0 0 0 0 0 0 0 0 0 0 Roach, percent TABLE 1 HF, mmg.

ppropriate abbreviations in 6 6 66 6 666 6 RV 6 6 o o m moo omooomwomomoww wmom mm 0 Q 0 00 60 066 6166 300 6606000660 6 6 0066 6 0061 00 0000000 000 0000000000 momo oooow mommuooo The following results wereobtained:

Approximate LD- values of carbamute phosphates Code N o.

and reported under the a Table 1.

on u Ame mnmm mamm a e 3 3 RRRR RRRR 7. The method of killing pestscomprising applying to a pest habitat a compound of claim 1. 50 8. Themethod of killing pests comprising applying to a pest habitat:beta-(QO-dimethyldithiophosphoryl)-ethylcarbamate.

9. The method of killing pests comprising applying to a pest habitat:

beta-(0,0-diethyldithiophosphoryl)-ethylcarbamate.

10. The method of killing pests comprising applying of d t 1 t g g}; toa pest habitat: sung an sum, an beta-(0,0-diethyldithiophosphoryl) ethylN,N-dimeththe gmuP i f i 'th 1 fkilli e t @0 risin a 1 in to loweralkenyl, lower a pes't g g 0 0 Hg P s 8 mp g ppy g Phenyl, Phen' beta(0,0-diethyldithiophosphoryl) ethyl-N,N-diethylcarbamate. 12. The methodof killing pests comprising applying horyn'ethylcarbamate' to a pesthabitat:

beta 0,0 diethylthionophosphoryl) ethyl 4 morpholinocarboxylate.

References Cited in the file of this patent UNITED STATES PATENTS2,862,019 Schrader Nov. 25, 1958 2,915,429 Scherer et a1. Dec. 1, 1959x=LD-50 considerably greater than 0.5% for insects and 0.06% [or mites.We claim: 1. As a new compound a carbamate phosphate of the formula (R0)a1 -Y RO0N hydrogen, lower alkyl chloro-substituted yl and a singlemorpholyl radical.

2. As a new compound: beta-(0,0-dimethyldithiophosp 3. As a newcompound: beta-(0,0-diethyldithiophosphoryl)-ethylcarbamate.

4. As a new compound: beta (0,0 diethyldithiophosphoryl) ethylN,N-dimethylcarbamate. 5. As a new compound:

thiophosphoryl) ethyl N,N diethylcarbamate.

wherein Y and Y are selected from the being sulfur, R is a lower alkylradical, R is the radical CH CH and R and R are selecte consisting ofalkyl-substituted phenyl beta (0,0-diethyldi

1. AS NEW COMPOUND A CARBAMATE PHOSPHATE OF THE FORMULA